arXiv subjects

Joachim Heberle

Publications and source records attributed to Joachim Heberle.

5 recordsLinked to original sources

arXiv2026

Microscopic Structure and Dynamics of Interfacial Water at Fluorinated vs Nonfluorinated Surfaces -- Insights from Ab-Initio Simulations and IR Spectroscopy

Per- and polyfluoroalkyl substances are a class of synthetic chemical compounds widely used as coatings to lower surface energies. Yet the microscopic mechanisms of their weak interaction with water and organic compounds remain poorly understood. Here, we perform large-scale density-functional-theory molecular dynamics simulations to investigate water at self-assembled monolayers (SAMs) of fluorinated and non-fluorinated hydrocarbons. We analyze the interfacial water structure and compare it to the prototypical hydrophobic air-water interface. The interfacial water structure at both SAMs closely resembles that at the air-water interface, featuring a distinct depletion layer and a two-dimensional hydrogen-bond network parallel to the surface. Computed anisotropic infrared spectra reproduce key experimental signatures observed in surface-enhanced infrared absorption spectroscopy (SEIRAS), including the presence of free OH vibrations directly probing the local surface-water interactions. Notably, while the free OH stretch at the hydrocarbon SAM-water interface exhibits a red shift relative to the air-water interface, indicative of weak binding, the fluorinated SAM-water interface displays a weakly blue-shifted free OH mode, in agreement with experiment. This frequency behavior defies common interpretations based on the vibrational Stark effect. Further, we show that the reorientation dynamics of water molecules are significantly slower near the fluorinated surface, which we correlate with spectral line shapes, an effect rather expected at hydrophilic surfaces. This indicates that fluorinated SAMs, despite being macroscopically more hydrophobic than their unfluorinated counterparts, exhibit spectroscopic characteristics that neither qualify it as hydrophobic nor hydrophilic.

physics.chem-ph↗

arXiv2025

Separate-scan atomic force microscope for fast infrared scattering-type scanning near-field optical microscope

Pseudo-heterodyne scattering-type scanning near-field optical microscopy (sSNOM) is applied in the mid-infrared region to detect the chemical composition of biomolecules on the nanoscale. However, the application of sSNOM in molecular biology has been limited to static images in air. Recently, bottom illumination sSNOM (BI-sSNOM) was developed for operation in water. Yet, the scan rate of sSNOM remains a bottleneck to record protein structural changes in aqueous solution on the seconds time scale. We designed an optical and mechanical system consisting of a separate scan high-speed atomic force microscope (HS-AFM) coupled to the BI-sSNOM optics. The designed AFM scanner has a mechanical bandwidth of ca 70 kHz along the Z-axis, and ca 6 kHz along the XY-axis, equivalent to the sample scanning HS-AFM. The AFM performance is demonstrated by imaging actin filaments. The optical design is validated by sSNOM experiments on purple membranes and microtubules.

physics.ins-det↗

arXiv2024

Evaluating aliphatic CF, CF2 and CF3 groups as vibrational Stark effect reporters

Given the extensive use of fluorination in molecular design, it is imperative to understand the solvation properties of fluorinated compounds and the impact of the C-F bond on electrostatic interactions. Vibrational spectroscopy can provide direct insight into these interactions by using the C-F bond stretching (v(C-F)) as an electric field probe through the vibrational Stark effect (VSE). In this work, we explore the VSE of the three basic patterns of aliphatic fluorination, i.e., mono-, di-, and trifluorination in CF, CF2 and CF3 groups, respectively, and compare their response to the well-studied aromatic v(C-F). Magnitudes (i.e. Stark tuning rates) and orientations of the difference dipole vectors of the v(C-F)-containing normal modes were determined using density functional theory and a molecular dynamics (MD)-assisted solvatochromic analysis of model compounds in solvents of varying polarity. We obtain Stark tuning rates of 0.2 - 0.8 cm-1/(MV/cm), with smallest and largest electric field sensitivities for CFaliphatic and CF3,aliphatic, respectively. While average electric fields of solvation were oriented along the main symmetry axis of the CFn, and thus along its static dipole, the Stark tuning rate vectors were tilted by up to 87 deg. potentially enabling to map electrostatics in multiple dimensions. We discuss the influence of conformational heterogeneity on spectral shifts and point out the importance of multipolar and/or polarizable MD force fields to describe the electrostatics of fluorinated molecules. The implications of this work are of direct relevance for studies of fluorinated molecules as found in pharmaceuticals, fluorinated peptides and proteins.

physics.chem-ph↗

arXiv2020

Magneto-Seebeck microscopy of domain switching in collinear antiferromagnet CuMnAs

Antiferromagnets offer spintronic device characteristics unparalleled in ferromagnets owing to their lack of stray fields, THz spin dynamics, and rich materials landscape. Microscopic imaging of aniferromagnetic domains is one of the key prerequisites for understading physical principles of the device operation. However, adapting common magnetometry techniques to the dipolar-field-free antiferromagnets has been a major challenge. Here we demonstrate in a collinear antiferromagnet a thermoelectric detection method by combining the magneto-Seebeck effect with local heat gradients generated by scanning far-field or near-field techniques. In a 20 nm epilayer of uniaxial CuMnAs we observe reversible 180 deg switching of the Néel vector via domain wall displacement, controlled by the polarity of the current pulses. We also image polarity-dependent 90 deg switching of the Néel vector in a thicker biaxial film, and domain shattering induced at higher pulse amplitudes. The antiferromagnetic domain maps obtained by our laboratory technique are compared to measurements by the established synchrotron microscopy using X-ray magnetic linear dichroism.

physics.app-ph↗

arXiv2019

Three-dimensional view of ultrafast dynamics in photoexcited bacteriorhodopsin

Bacteriorhodopsin (bR) is a light-driven proton pump. We use time-resolved crystallography at an X-ray free-electron laser to follow the structural changes in multiphoton-excited bR from 250 femtoseconds to 10 picoseconds. Quantum chemistry and ultrafast spectroscopy allow identifying a sequential two-photon absorption process, leading to excitation of a tryptophan residue flanking the retinal chromophore, as a first manifestation of multi-photon effects. We resolve distinct stages in the structural dynamics of the all-trans retinal in photoexcited bR to a highly twisted 13-cis conformation. Other active site sub-picosecond rearrangements include correlated vibrational motions of the electronically excited retinal chromophore, the surrounding amino acids and water molecules as well as their hydrogen bonding network. These results show that this extended photo-active network forms an electronically and vibrationally coupled system in bR, and most likely in all retinal proteins.

physics.bio-ph↗